Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/32—Post-polymerisation treatment
  • C08G77/34—Purification
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/18—Block or graft polymers
  • C08G64/186—Block or graft polymers containing polysiloxane sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
  • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/06—Preparatory processes
  • C08G77/08—Preparatory processes characterised by the catalysts used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/346—Clay
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica

Definitions

• the present invention relates to a polyorganosiloxane to be used as a raw material for a polycarbonate-polyorganosiloxane copolymer, and to a polycarbonate-polyorganosiloxane copolymer obtained by using the polyorganosiloxane.
• a polycarbonate is excellent in mechanical properties such as transparency and impact resistance, and hence has been widely utilized in industries typified by an automobile field, an OA field, and electrical and electronic fields.
• a homopolycarbonate using 2,2-bis(4-hydroxyphenyl)propane [common name: bisphenol A] as a dihydric phenol serving as a raw material has been generally used as a typical polycarbonate.
• a polycarbonate-polyorganosiloxane copolymer using a polyorganosiloxane as a copolymerizable monomer has been known for improving the physical properties of the homopolycarbonate such as flame retardancy and impact resistance (see Patent Documents 1 to 3).
• a polyorganosiloxane obtained by: causing a siloxane having a cyclic structure such as octamethylcyclotetrasiloxane and a disiloxane such as tetramethyldisiloxane to react with each other to produce a linear dimethylsiloxane; and causing a hydrogen atom at a terminal of the dimethylsiloxane to react with a phenolic compound such as 2-allylphenol or eugenol in the presence of a platinum chloride-alcoholate complex as a catalyst (see Patent Documents 4 to 6).
• a reaction mixture needs to be subjected to oil-water separation into an organic phase formed of an organic solvent (such as methylene chloride) containing the polycarbonate-polyorganosiloxane copolymer and an aqueous phase containing unreacted bisphenol A and an amine compound used in a polymerization catalyst.
• an organic solvent such as methylene chloride
• the organic phase and the aqueous phase need to be subjected to oil-water separation from each other.
• an object of the present invention is to provide the following polyorganosiloxane and a polycarbonate-polyorganosiloxane copolymer obtained by using the polyorganosiloxane.
• the polyorganosiloxane is used as a raw material for a polycarbonate-polyorganosiloxane copolymer, an oil-water separation rate in the step of purifying the polycarbonate-polyorganosiloxane copolymer is high.
• the inventors of the present invention have made extensive investigations, and as a result, have found that platinum used as a catalyst at the time of the production of a polyorganosiloxane remains in the polyorganosiloxane, which results in an adverse effect on separation between an organic phase and an aqueous phase upon production of a polycarbonate-polyorganosiloxane copolymer through the use of the polyorganosiloxane as a raw material by an interfacial polymerization method.
• the present invention has been made on the basis of such finding.
• the present invention relates to a polyorganosiloxane and a polycarbonate-polyorganosiloxane copolymer according to the following items 1 to 10.
• R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms
• Y represents a single bond, or an organic residue containing an aliphatic or aromatic moiety, the organic residue being bonded to Si and O or to Si and Z
• n represents an average number of repetitions
• m represents 0 or 1
• Z each independently represent a halogen, —R 5 OH, —R 5 COOH, —R 5 NH 2 , —R 5 NHR 6 , —COOH, or —SH
• R 5 represents a linear, branched, or cyclic alkylene group, an aryl-substituted alkylene group, an aryl-substituted alkylene group that may have an alkoxy group on a ring thereof, or an arylene group
• R 6
• R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, n represents an average number of repetitions, and a represents a positive integer.
• R 11 to R 14 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms
• Y 1 represents a single bond, or an organic residue containing an aliphatic or aromatic moiety
• n1 represents an average number of repetitions
• R 21 and R 22 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms
• X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an
• the polyorganosiloxane of the present invention has a small platinum content, and hence when a polycarbonate-polyorganosiloxane copolymer is produced by using the polyorganosiloxane, an oil-water separation rate in the step of purifying the polycarbonate-polyorganosiloxane copolymer is high. Accordingly, the polycarbonate-polyorganosiloxane copolymer can be efficiently produced by using the polyorganosiloxane of the present invention.
• a polyorganosiloxane of the present invention has a platinum content of 1 ppm by mass or less, preferably 0.5 ppm by mass or less, more preferably 0.2 ppm by mass or less.
• the platinum content in the polyorganosiloxane is 1 ppm by mass or less, an oil-water separation rate in the step of purifying a polycarbonate-polyorganosiloxane copolymer upon production of the polycarbonate-polyorganosiloxane copolymer through the use of the polyorganosiloxane can be increased.
• the platinum content in the polyorganosiloxane is 1 ppm by mass or less, the hue of the polyorganosiloxane improves.
• a situation where the hue of the polyorganosiloxane improves is assumed to mean that the oxidative deterioration of the polyorganosiloxane has been reduced.
• a situation where the hue of the polyorganosiloxane is bad is assumed to mean that the oxidative deterioration of the polyorganosiloxane is progressing.
• an improving effect on the hue of the molded article is expected. That is, in the case where the polyorganosiloxane of the present invention is used, the hue of the molded article is expected to improve as compared to the case where a polyorganosiloxane having a bad hue is used as an additive.
• the polyorganosiloxane of the present invention may contain platinum.
• the polyorganosiloxane of the present invention is preferably produced by using a platinum-based catalyst.
• the polyorganosiloxane of the present invention preferably has a repeating unit represented by the following general formula (1).
• R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
• Examples of the halogen atom represented by R 1 or R 2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• Examples of the alkyl group represented by R 1 or R 2 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, various butyl groups (“various” means that a linear group and any branched group are included, and the same shall apply hereinafter), various pentyl groups, and various hexyl groups.
• An example of the alkoxy group represented by R 1 or R 2 is an alkoxy group whose alkyl group moiety is the alkyl group described above.
• Examples of the aryl group represented by R 1 or R 2 include a phenyl group and a naphthyl group.
• R 1 and R 2 each preferably represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and each more preferably represent a methyl group.
• the polyorganosiloxane of the present invention is preferably represented by the following general formula (1-1).
• R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms
• Y represents a single bond, or an organic residue containing an aliphatic or aromatic moiety, the organic residue being bonded to Si and O or to Si and Z
• n represents an average number of repetitions
• m represents 0 or 1
• Z each independently represent a halogen, —R 5 OH, —R 5 COOH, —R 5 NH 2 , —R 5 NHR 6 , —COOH, or —SH
• R 5 represents a linear, branched, or cyclic alkylene group, an aryl-substituted alkylene group, an aryl-substituted alkylene group that may have an alkoxy group on a ring thereof, or an arylene group
• R 6
• R 1 and R 2 are as described above, and R 3 and R 4 are the same as R 1 and R 2 .
• R 1 to R 4 each preferably represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and each more preferably represent a methyl group.
• Y represents a single bond, or an organic residue containing an aliphatic or aromatic moiety, the organic residue being bonded to Si and O or to Si and Z.
• n represents an average number of repetitions and is preferably 10 to 1,000. It should be noted that a value for the average number of repetitions n is a value calculated by nuclear magnetic resonance (NMR) measurement.
• NMR nuclear magnetic resonance
• Z preferably represents —R 5 OH, —R 5 COOH, —R 5 NH 2 , —R 5 NHR 6 , —COOH, or —SH.
• the R 5 represents a linear, branched, or cyclic alkylene group, an aryl-substituted alkylene group, an aryl-substituted alkylene group that may have an alkoxy group on a ring thereof, or an arylene group
• R 6 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group.
• Z preferably represents a residue of a phenol-based compound having an alkyl group, and more preferably represents an organic residue derived from allylphenol or an organic residue derived from eugenol.
• Examples of the polyorganosiloxane represented by the general formula (1-1) include compounds represented by the following general formulae (1-2) to (1-12).
• R 1 to R 4 , R 6 , and n are as described above, and preferred ones thereof are also the same as those described above.
• a represents a positive integer and typically represents an integer of 1 to 6.
• a phenol-modified polyorganosiloxane represented by the general formula (1-2) is preferred from the viewpoint of the ease of polymerization upon production of the polycarbonate-polyorganosiloxane copolymer.
• ⁇ , ⁇ -bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane as one kind of the compounds each represented by the general formula (1-3) or ⁇ , ⁇ -bis[3-(4-hydroxy-3-methoxyphenyl)propyl]polydimethylsiloxane as one kind of the compounds each represented by the general formula (1-4) is preferred.
• the polyorganosiloxane of the present invention can be obtained by first obtaining a crude polyorganosiloxane having a platinum content of more than 1 ppm by mass according to a known production method, and then removing platinum in the crude polyorganosiloxane with a porous adsorbent.
• a method of producing the crude polyorganosiloxane is not particularly limited.
• the crude polyorganosiloxane can be obtained by: causing cyclotrisiloxane and disiloxane to react with each other in the presence of an acid catalyst to synthesize ⁇ , ⁇ -dihydrogen organopentasiloxane; and then subjecting the ⁇ , ⁇ -dihydrogen organopentasiloxane to an addition reaction with a phenolic compound (such as 2-allylphenol, 4-allylphenol, eugenol, or 2-propenylphenol) or the like in the presence of a catalyst for a hydrosilylation reaction.
• a phenolic compound such as 2-allylphenol, 4-allylphenol, eugenol, or 2-propenylphenol
• the crude polyorganosiloxane can be obtained by: causing octamethylcyclotetrasiloxane and tetramethyldisiloxane to react with each other in the presence of sulfuric acid (acid catalyst); and subjecting the resultant ⁇ , ⁇ -dihydrogen organopolysiloxane to an addition reaction with a phenolic compound or the like in the presence of the catalyst for a hydrosilylation reaction in the same manner as in the above.
• chain length n of the ⁇ , ⁇ -dihydrogen organopolysiloxane can be appropriately adjusted depending on a polymerization condition before its use, or a commercially available ⁇ , ⁇ -dihydrogen organopolysiloxane may be used.
• a platinum-based catalyst is generally used as the catalyst for a hydrosilylation reaction in terms of a reaction rate and selectivity.
• Specific examples of the platinum-based catalyst include chloroplatinic acid, a solution of chloroplatinic acid in an alcohol, an olefin complex of platinum, a complex of platinum and a vinyl group-containing siloxane, platinum-supported silica, and platinum-supported activated carbon.
• the porous adsorbent is caused to adsorb platinum in the crude polyorganosiloxane obtained by using the platinum-based catalyst as the catalyst for a hydrosilylation reaction
• the polyorganosiloxane of the present invention having a platinum content of 1 ppm by mass or less, preferably 0.5 ppm by mass or less, more preferably 0.2 ppm by mass or less can be obtained. It should be noted that the polyorganosiloxane of the present invention may contain platinum.
• the platinum content in the polyorganosiloxane in the present invention is measured with an ICP emission analyzer and is specifically measured by a method described in Examples.
• the average pore diameter of the porous adsorbent is preferably 1,000 ⁇ or less, more preferably 500 ⁇ or less, still more preferably 200 ⁇ or less, yet still more preferably 150 ⁇ or less, particularly preferably 100 ⁇ or less from the viewpoint of efficiently removing platinum.
• the porous adsorbent is not particularly limited as long as the adsorbent has the above-mentioned average pore diameter.
• activated clay for example, there can be used activated clay, acid clay, activated carbon, synthetic zeolite, natural zeolite, activated alumina, silica, a silica-magnesia-based composite adsorbent, diatomaceous earth, and cellulose.
• the average particle diameter of the porous adsorbent is measured with an automatic gas adsorption measuring device, and is specifically measured by a method described in Examples.
• the average particle diameter of the porous adsorbent is typically 1 ⁇ m to 4 mm, preferably 1 ⁇ m to 100 ⁇ m.
• the usage amount of the porous adsorbent is not particularly limited. However, the usage amount of the porous adsorbent falls within the range of preferably 1 part by mass to 30 parts by mass, more preferably 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the crude polyorganosiloxane.
• the porous adsorbent After the porous adsorbent has been caused to adsorb platinum in the crude polyorganosiloxane, the porous adsorbent can be separated from the polyorganosiloxane by any separating means.
• the means for separating the porous adsorbent from the polyorganosiloxane include a filter and centrifugation.
• a filter such as a membrane filter, a sintered metal filter, or a glass fiber filter can be used.
• the membrane filter is particularly preferably used.
• the polyorganosiloxane to be treated when the crude polyorganosiloxane to be treated has so high a molecular weight that the crude polyorganosiloxane is not in a liquid state, the polyorganosiloxane may be heated to such a temperature as to be in a liquid state upon performance of the adsorption with the porous adsorbent and the separation of the porous adsorbent. Alternatively, the adsorption and the separation may be performed in a state in which the polyorganosiloxane is dissolved in a solvent such as methylene chloride or hexane.
• a solvent such as methylene chloride or hexane.
• the polyorganosiloxane of the present invention can be suitably used in the production of a polycarbonate-polyorganosiloxane copolymer (hereinafter sometimes abbreviated as “PC-POS copolymer”).
• PC-POS copolymer a polycarbonate-polyorganosiloxane copolymer
• a known production method such as an interfacial polymerization method (phosgene method), a pyridine method, or an ester exchange method can be employed as a method of producing the PC-POS copolymer of the present invention.
• the step of separating an organic phase containing the PC-POS copolymer and an aqueous phase containing an unreacted substance, a catalyst residue, or the like becomes easy, and hence the separation of the organic phase containing the PC-POS copolymer and the aqueous phase in each washing step such as alkali washing, acid washing and pure water washing becomes easy. Accordingly, the PC-POS copolymer is efficiently obtained.
• the PC-POS copolymer obtained by using the polyorganosiloxane of the present invention is of high quality because the copolymer has a small amount of a catalyst residue derived from the platinum-based catalyst in the copolymer.
• the PC-POS copolymer of the present invention has a platinum content of 0.4 ppm by mass or less, preferably 0.2 ppm by mass or less, more preferably 0.08 ppm by mass or less, still more preferably 0.06 ppm by mass or less. It should be noted that the platinum content in the PC-POS copolymer is measured with an ICP emission analyzer as in the measurement of the platinum content in the polyorganosiloxane.
• the PC-POS copolymer of the present invention preferably includes a polyorganosiloxane moiety as a repeating unit having a structure represented by the following general formula (I) and a polycarbonate moiety as a repeating unit having a structure represented by the following general formula (II).
• R 11 to R 14 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms
• Y 1 represents a single bond, or an organic residue containing an aliphatic or aromatic moiety
• n1 represents an average number of repetitions
• R 21 and R 22 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms
• X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms,
• R 11 to R 14 , Y 1 , and n1 are the same as R 1 to R 4 , Y, and n in the general formula (1-1), and a preferred ones thereof are also the same as those in the above.
• a method of producing the PC-POS copolymer is not particularly limited and the copolymer can be produced with reference to a known method of producing a PC-POS copolymer such as a method described in JP 2010-241943 A.
• the PC-POS copolymer can be produced by: dissolving an aromatic polycarbonate oligomer produced in advance and the polyorganosiloxane of the present invention in a water-insoluble organic solvent (such as methylene chloride); adding an aqueous solution of a dihydric phenol-based compound (such as bisphenol A) in an alkaline compound (such as aqueous sodium hydroxide) to the solution; and subjecting the mixture to an interfacial polycondensation reaction through the use of a tertiary amine (such as triethylamine) or a quaternary ammonium salt (such as trimethylbenzylammonium chloride) as a polymerization catalyst in the presence of a terminal stopper (a monohydric phenol such as p-t-butylphenol).
• the PC-POS copolymer can also be produced by copolymerizing a polyorganosiloxane, a dihydric phenol, and phosgene,
• the polyorganosiloxane represented by the general formula (1-1) is preferably used as the polyorganosiloxane. It should be noted that the content of the repeating unit containing a structure represented by the general formula (I) can be adjusted by, for example, adjusting the usage amount of the polyorganosiloxane represented by the general formula (1-1).
• the polycarbonate oligomer can be produced through a reaction of a dihydric phenol and a carbonate precursor such as phosgene in an organic solvent such as methylene chloride, chlorobenzene, or chloroform.
• a carbonate precursor such as phosgene
• an organic solvent such as methylene chloride, chlorobenzene, or chloroform.
• the oligomer can also be produced through a reaction of a dihydric phenol and a carbonate precursor such as diphenyl carbonate.
• a dihydric phenol represented by the following general formula (2) is preferably used as the dihydric phenol.
• R 21 , R 22 , X, b, and c are as described above.
• Examples of the dihydric phenol represented by the general formula (2) include bis(hydroxyphenyl)alkane dihydric phenols such as 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4′-dihydroxydiphenyl, a bis(4-hydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, and bis(4-hydroxyphenyl)ketone.
• bis(hydroxyphenyl)alkane dihydric phenols such as 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane, 1,1
• bis(hydroxyphenyl)alkane dihydric phenols are preferred, and bisphenol A is more preferred.
• dihydric phenol other than bisphenol A examples include a bis(hydroxyaryl)alkane, a bis(hydroxyaryl)cycloalkane, a dihydroxyaryl ether, a dihydroxydiaryl sulfide, a dihydroxydiaryl sulfoxide, a dihydroxydiaryl sulfone, a dihydroxydiphenyl, a dihydroxydiarylfluorene, and a dihydroxydiaryladamantane.
• One of those dihydric phenols may be used alone, or two or more thereof may be used as a mixture.
• bis(hydroxyaryl)alkane examples include bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, bis(4-hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxy-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, and 2,2-2-
• Examples of the bis(hydroxyaryl)cycloalkane include 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)norbornane, and 1,1-bis(4-hydroxyphenyl)cyclododecane.
• Examples of the dihydroxyaryl ether include 4,4′-dihydroxyphenyl ether and 4,4′-dihydroxy-3,3′-dimethylphenyl ether.
• dihydroxydiaryl sulfide examples include 4,4′-dihydroxydiphenyl sulfide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide.
• dihydroxydiaryl sulfoxide examples include 4,4′-dihydroxydiphenyl sulfoxide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide.
• dihydroxydiaryl sulfone examples include 4,4′-dihydroxydiphenyl sulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone.
• dihydroxydiphenyl is 4,4′-dihydroxydiphenyl.
• dihydroxydiarylfluorene include 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene.
• dihydroxydiaryladamantane include 1,3-bis(4-hydroxyphenyl)adamantane, 2,2-bis(4-hydroxyphenyl)adamantane, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.
• dihydric phenol other than the above examples include 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisphenol, 10,10-bis(4-hydroxyphenyl)-9-anthrone, and 1,5-bis(4-hydroxyphenylthio)-2,3-dioxapentane.
• the PC-POS copolymer can be produced by copolymerizing the dihydric phenol represented by the general formula (2), a polyorganosiloxane represented by the following general formula (3), and phosgene, a carbonate, or a chloroformate.
• the polyorganosiloxane represented by the following general formula (3) is a product of a reaction between the polyorganosiloxane represented by the general formula (1-1) and a diisocyanate compound.
• R 1 to R 4 , n, m, Y, and Z are as defined in the above, and preferred ones thereof are also the same as those in the above.
• Z 1 represents a divalent group derived from Z in the polyorganosiloxane represented by the general formula (1-1) after the reaction of the Z with a —NCO group in the diisocyanate compound.
• ⁇ represents a divalent group derived from the diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide, and examples thereof include divalent groups each represented by any one of the following general formulae (3-1) to (3-5).
• a terminal stopper In order to control the molecular weight of the PC-POS copolymer to be obtained, a terminal stopper can be used.
• the terminal stopper may include monohydric phenols such as phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, and p-tert-amylphenol.
• monohydric phenols such as phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, and p-tert-amylphenol.
• One of those monohydric phenols may be used alone, or two or more thereof may be used in combination.
• n (a degree of polymerization) representing the chain length of the polyorganosiloxane represented by the general formula (1-1) is typically about 10 to 1,000, and from the viewpoints of an improvement in impact strength of the copolymer, workability, and the acquisition of excellent flame retardancy, is preferably 30 to 600, more preferably 40 to 300, still more preferably 40 to 200.
• n 10 or more, an improving effect on the impact strength becomes sufficient, and when n is 1,000 or less, handleability upon production of the PC-POS copolymer becomes satisfactory, which eliminates such a risk that the workability is impaired.
• the PC-POS copolymer of the present invention can be produced by appropriately using, for example, a molecular weight modifier so that its viscosity-average molecular weight may be a molecular weight intended for an application or product in which the copolymer is used.
• the copolymer is produced so as to have a viscosity-average molecular weight in the range of typically about 14,000 to 23,000, preferably about 15,000 to 22,000.
• the viscosity-average molecular weight is 14,000 or more, the rigidity and impact strength of a molded body become sufficient, and when the molecular weight is 23,000 or less, the viscosity of the PC-POS copolymer does not become excessively large and hence the productivity at the time of its production becomes satisfactory. In addition, there is no risk in that it becomes difficult to mold the copolymer into a thin body.
• the resultant is appropriately left at rest to be separated into an aqueous phase and a water-insoluble organic solvent phase [separating step], the water-insoluble organic solvent phase is washed (preferably washed with a basic aqueous solution, an acidic aqueous solution, and water in the stated order) [washing step], and the resultant organic phase is concentrated [concentrating step], pulverized [pulverizing step], and dried [drying step].
• the PC-POS copolymer can be obtained.
• oil-water separation rates in the separating step and the washing step are high, and hence the PC-POS copolymer can be efficiently produced.
• An adsorbent was subjected to a vacuum evacuation treatment at 200° C. for 3 hours, and its average pore diameter was measured with a pore analyzer (“AUTOSORB-3” manufactured by Quantachrome Instruments) by a constant volume method (nitrogen adsorption).
• a platinum content in a sample was measured as described below. After organic matter in a PDMS-PC had been subjected to a sulfuric acid ashing treatment, the residue was dissolved in hydrofluoric acid and aqua regia, and the solution was subjected to the measurement with an ICP emission analyzer (manufactured by Hitachi High-Tech Science Corporation, trade name: “SPS5100”) under the measurement conditions of a calibration curve method.
• an ICP emission analyzer manufactured by Hitachi High-Tech Science Corporation, trade name: “SPS5100”
• the platinum content in the PDMS after the purification represents the platinum content in the PDMS after the purification of a crude polyorganosiloxane with an adsorbent in each of Examples 1 to 6, and represents the platinum content in the PDMS after the purification of the crude polyorganosiloxane with a filter made of polypropylene in Comparative Example 2.
• the platinum content in the PDMS before the purification represents the platinum content in the PDMS measured in Comparative Example 1.
• a hue was visually evaluated by using an APHA standard color.
• a water content in an organic phase after oil-water separation was measured by titrating water with a water vaporizer (“Model VA-100” manufactured by Mitsubishi Chemical Corporation) and a trace water-measuring apparatus (“Model CA-100” manufactured by Mitsubishi Chemical Corporation) according to Karl Fischer titration.
• the measurement was performed under the following measurement conditions: the flow rate of a nitrogen gas in the water vaporizer was 250 ml/min and the temperature of the heating furnace of the water vaporizer was 230° C.
• the product thus obtained was dissolved in 10 L of methylene chloride. After that, the solution was washed with 1.5 L of 0.3 mol/L aqueous NaOH twice, washed with 1.5 L of 2 mass % phosphoric acid for neutralization, and further washed with water once. Methylene chloride was removed by concentration at 30° C. to 40° C. under reduced pressure, and methylene chloride was further removed under reduced pressure at 60° C. Thus, a 2-allylphenol terminal-modified PDMS (crude PDMS) was obtained.
• the structure and composition of the resultant crude PDMS were analyzed by 1 H-NMR. As a result, the number of repetitions of the dimethylsiloxy unit of the resultant 2-allylphenol terminal-modified PDMS was 40. In addition, a platinum content in the crude PDMS was 2.0 ppm by mass.
• the activated clay used as the adsorbent was suction-filtered with a membrane filter (manufactured by ADVANTEC, filter paper made of polytetrafluoroethylene, pore diameter: 0.2 ⁇ m). Thus, a filtrate was obtained. Methylene chloride was removed by concentrating the filtrate, and then the residue was dried under a vacuum to provide a 2-allylphenol terminal-modified PDMS (PDMS-1). A platinum content in the 2-allylphenol terminal-modified PDMS was 0.1 ppm by mass. A platinum removal ratio by the purification was 95 mass %. The APHA of the purified polyorganosiloxane was 25. The results are shown in Table 1.
• Polyorganosiloxanes (PDMS-2 to PDMS-6) were each produced by using the crude PDMS produced in the section (1) of Example 1 (platinum content: 2.0 ppm by mass) in the same manner as in Example 1 except that an adsorbent shown in Table 1 was used as an adsorbent instead of the activated clay, and the polyorganosiloxanes were subjected to similar measurements. The results are shown in Table 1.
• Acid clay manufactured by Mizusawa Industrial Chemicals, Ltd., trade name: “MIZUKA ACE #20”, average pore diameter: 108 ⁇
• Synthetic zeolite manufactured by Mizusawa Industrial Chemicals, Ltd., trade name: “MIZUKASIEVES EX-122”, average pore diameter: 19 ⁇
• Activated alumina manufactured by Mizusawa Industrial Chemicals, Ltd., trade name: “ACTIVATED ALUMINA GP-20”, average pore diameter: 111 ⁇
• a polyorganosiloxane (PDMS-7) was produced by using the crude PDMS produced in the section (1) of Example 1 (platinum content: 2.0 ppm by mass) in the same manner as in Example 1 except that no adsorbent was used, and the polyorganosiloxane was subjected to similar measurements. The results are shown in Table 1.
• a tubular filter made of polypropylene having an inner diameter of 8.5 cm and a length of 12.5 cm (“BFP-410-1” manufactured by Taki Engineering Co., Ltd.) was set in a cylindrical glass vessel having an inner diameter of 10 cm and a height of 18 cm.
• 20 g of the crude PDMS produced in the section (1) of Example 1 platinum content: 2.0 ppm by mass was flowed into the filter to provide a filtrate as a polyorganosiloxane (PDMS-8). After that, similar measurements were performed. The results are shown in Table 1.
• BPA sodium dithionite with respect to bisphenol A
• the solution of BPA in aqueous sodium hydroxide, methylene chloride, and phosgene were continuously passed through a tubular reactor having an inner diameter of 6 mm and a tube length of 30 m at flow rates of 40 L/h, 15 L/h, and 4.0 kg/h, respectively.
• the tubular reactor had a jacket portion and the temperature of a reaction liquid was kept at 40° C. or less by passing cooling water through the jacket.
• the reaction liquid that had exited the tubular reactor was continuously introduced into a baffled vessel-type reactor having an internal volume of 40 L provided with a sweptback blade, and then the solution of BPA in aqueous sodium hydroxide, 25 mass aqueous sodium hydroxide, water, and a 1 mass % aqueous solution of triethylamine were further added to the reactor at flow rates of 2.8 L/h, 0.07 L/h, 17 L/h, and 0.64 L/h, respectively, to thereby perform a reaction.
• the reaction liquid flowing out of the vessel-type reactor was continuously taken out, and then an aqueous phase was separated and removed by leaving the liquid at rest, followed by the collection of a methylene chloride phase. Thus, a polycarbonate oligomer solution was obtained.
• the polycarbonate oligomer solution had a polycarbonate oligomer concentration of 318 g/L.
• a chloroformate group concentration in the polycarbonate oligomer was 0.75 mol/L. It should be noted that the chloroformate group concentration was determined from 1 H-NMR analysis.
• the polycarbonate oligomer had a weight-average molecular weight (Mw) of 1,190.
• the weight-average molecular weight (Mw) of the polycarbonate oligomer was measured as a molecular weight by using the polystyrene calibration curve according to GPC using tetrahydrofuran as a developing solvent under the following conditions.
• the polymerization liquid thus obtained was filled into a cylindrical glass container having an inner diameter of 4.2 cm and a height of 40 cm. After a lapse of a predetermined time, an organic phase (methylene chloride solution containing the polycarbonate-polyorganosiloxane copolymer) at a position corresponding to a height of 20 cm from the bottom was collected, and a water content in the organic phase was measured by the method. A relational expression between an elapsed time and the remaining water content in the organic phase was determined by plotting the remaining water content in the organic phase at each elapsed time, and a time (min) required for the water content in the organic phase to reach 2.8 mass % was determined from the relational expression.
• an organic phase methylene chloride solution containing the polycarbonate-polyorganosiloxane copolymer
• Aqueous NaOH was added to the organic phase obtained in the polymerization liquid-separating step so that the content of the aqueous phase became 15 vol %, and the mixture was stirred at 350 rpm for 10 minutes.
• the solution obtained after the stirring was filled into a cylindrical glass vessel having an inner diameter of 4.2 cm and a height of 40 cm. After a lapse of a predetermined time, an organic phase (methylene chloride solution containing the polycarbonate-polyorganosiloxane copolymer) at a position corresponding to a height of 20 cm from the bottom was collected, and a water content in the organic phase was measured by the method.
• a relational expression between an elapsed time and the remaining water content in the organic phase was determined by plotting the remaining water content in the organic phase at each elapsed time, and a time (min) required for the water content in the organic phase to reach 1.5 mass % was determined from the relational expression.
• Aqueous HCl was added to the organic phase obtained in the aqueous NaOH washing step so that the content of the aqueous phase became 15 vol %, and the mixture was stirred at 500 rpm for 10 minutes.
• the solution obtained after the stirring was filled into a cylindrical glass vessel having an inner diameter of 4.2 cm and a height of 40 cm. After a lapse of a predetermined time, an organic phase (methylene chloride solution containing the polycarbonate-polyorganosiloxane copolymer) at a position corresponding to a height of 20 cm from the bottom was collected, and a water content in the organic phase was measured by the method.
• a relational expression between an elapsed time and the remaining water content in the organic phase was determined by plotting the remaining water content in the organic phase at each elapsed time, and a time (min) required for the water content in the organic phase to reach 1.5 mass % was determined from the relational expression.
• Pure water was added to the organic phase obtained in the aqueous HCl washing step so that the content of the aqueous phase became 15 vol %, and the mixture was stirred at 500 rpm for 10 minutes.
• the solution obtained after the stirring was filled into a cylindrical glass vessel having an inner diameter of 4.2 cm and a height of 30 cm. After a lapse of a predetermined time, an organic phase (methylene chloride solution containing the polycarbonate-polyorganosiloxane copolymer) at a position corresponding to a height of 20 cm from the bottom was collected, and a water content in the organic phase was measured by the method.
• a relational expression between an elapsed time and the remaining water content in the organic phase was determined by plotting the remaining water content in the organic phase at each elapsed time, and a time (min) required for the water content in the organic phase to reach 1.5 mass % was determined from the relational expression.
• Copolymers were each produced in the same manner as in Example 7 except that in Example 7, any one of the PDMS-2 to the PDMS-8 was used instead of the PDMS-1, washing and oil-water separation were performed, and a time required for a water content in an organic phase to reach a predetermined value in each step was determined. The results are shown in Table 2.
• the polyorganosiloxane of the present invention has a small platinum content, and hence when a polycarbonate-polyorganosiloxane copolymer is produced by using the polyorganosiloxane, an oil-water separation rate in the step of purifying the polycarbonate-polyorganosiloxane copolymer is high. Accordingly, the polycarbonate-polyorganosiloxane copolymer can be efficiently produced by using the polyorganosiloxane of the present invention.

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